CN105504135A - Method for preparing sodium salt derivative of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid copolymer - Google Patents
Method for preparing sodium salt derivative of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid copolymer Download PDFInfo
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- CN105504135A CN105504135A CN201511016311.8A CN201511016311A CN105504135A CN 105504135 A CN105504135 A CN 105504135A CN 201511016311 A CN201511016311 A CN 201511016311A CN 105504135 A CN105504135 A CN 105504135A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
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Abstract
The invention discloses a method for preparing a sodium salt derivative of an acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid copolymer. A specific synthesis method comprises the following steps: (1) adding acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, an RAFT (Reversible Addition-Fragmentation Chain Transfer) reagent and deionized water into a reactor, and stirring till the materials are dissolved; (2) heating to 50-70 DEG C, and dropwise adding a persulfide aqueous solution slowly; (3) continually stirring for 5-8 hours after the end of dropwise adding; (4) adding a NaOH aqueous solution into the reactor, adjusting the pH to 8-9, and performing rotary evaporation to remove a solvent in order to obtain a product. The sodium salt derivative of the acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid copolymer prepared through the method has a number-average molecular weight of 5,200-10,000, and molecular weight distribution of between 1.60 and 1.85.
Description
Technical field
The present invention relates to a kind of preparation method of binary polymer, particularly relate to and a kind ofly prepare the vinylformic acid of narrow molecular weight distributions and the method for 2-acrylamide-2-methyl-propane sulfonic acid multipolymer sodium salt derivative.
Background technology
Polymkeric substance containing hydroxy-acid group and sulfonic acid group due in molecular structure containing strong anionic property functional group, weak anionic functional group simultaneously containing strong sequestering power, makes it have excellent water-soluble, good dispersive ability, complex ability and antifouling capability.2-acrylamide-2-methyl-propane sulfonic acid (2-Acrylamide-2-MethylPropaneSulfonicacid, AMPS) containing one the most common in the monomer of sulfonic acid group.Structure is as follows.
The synthesis of AMPS starts from 1961, and the progressively suitability for industrialized production such as Lubrizol company of the twentieth century U.S. at the beginning of the seventies, Rhom and Hass, Dong chemical company, synthesis main raw material is iso-butylene, sulfonated reagent, vinyl cyanide.
The multipolymer of AMPS and vinylformic acid (AA) studies the most deeply and a kind of polymkeric substance containing hydroxy-acid group and sulfonic acid group widely.US3332904 discloses the terpolymer of AMPS, vinyl cyanide and acrylic acid derivative prepared by organic solvent system, declares its molecular weight OK range 600 to 4000.Prepared by use Raolical polymerizable, its initiator is azo diisobutyl nitrile (AIBN).US3898037 and US3806367 discloses the multipolymer of aqueous phase AMPS and vinyl monomer (comprising vinylformic acid, acrylamide, toxilic acid and derivative thereof), declares that molecular weight of copolymer is 1000 to 10000.Its initiator is azo diisobutyl nitrile or hydrogen peroxide.Dow company (former ROHM AND HAAS) reports the multipolymer containing carboxylate radical and sulfonate radical in patent CN101597549A, and the terpolymer of nonionic monomers is applied in dish washing detergent compositions.This patent adopts the method for aqueous phase free radical polyalcohol to prepare multipolymer, comonomer I is vinylformic acid, monomer II is that AMPS, monomer II I are selected from ethyl propenoate (EA), N-tert-butyl acrylamide (tBAM) and (methyl) Propylene glycol monoacrylate (HPA).According to embodiment introduction, in copolymer molecule, acrylic acid content is 65% to 70%, AMPS content is 15% to 30%.Molecular weight of copolymer is more than 30,000.Kao Corp reports the multipolymer of AA and AMPS at patent CN100503802C, and reaction system is aqueous phase, and initiator is azo-bis-isobutyrate hydrochloride.Average molecular weight of copolymer more than 1,500,000.LG house journal CN101617034B reports the powder detergent of the multipolymer using vinylformic acid and AMPS.The ratio of AA and AMPS is 95:5 to 80:20, and reaction system is aqueous phase, and initiator is persulphate.Guangzhou Xing Ye company reports the preparation of toxilic acid (acid anhydride)/AA/AMPS ter-polymers at patent CN101362811B, and described catalyzer is manganous sulfate or neutralized verdigris; Consumption is 0.5 to 50ppm.Described initiator is the composition of persulphate and hydrogen peroxide; The weight-average molecular weight of multipolymer is between 1000 to 30000.
As mentioned above, disclosed in current patent and document, AA and AMPS molecular weight distribution is broad, does not carry out refinement and control to the distribution of molecular weight.Multipolymer prepared by a lot of document is conceived to control comonomer ratio, obtains the multipolymer that group numbers is controlled; And investigate its impact for application performance.Substantially do not have document and report to relate to and how to prepare narrow molecular weight distribution, and the multipolymer of AA and AMPS of number-average molecular weight lower (lower than 10,000).
For polymkeric substance, there is the homologue of a large amount of structural similitude in the polymkeric substance of molecular weight broadness, there is the uncontrollable characteristic of composition.The component that molecular weight is larger easily affects its solubility property in aqueous, and then affects its cleaning product use properties; And the component of molecular weight is water-soluble excessively strong, the avidity for lyophobic dust is more weak.Therefore, be necessary to adopt different processing condition, the AA of synthesis different molecular weight (especially molecular weight is below 10,000) and narrow ditribution and AMPS copolymer, meet the needs in application.
RAFT (reversible addion-fragmentation chain transfer) polymerization process be add in traditional radical polymerization there is high chain transfer constant and ad hoc structure two sulfur esters as chain-transfer agent.The spike of RAFT process comes from the thermolysis of classical initiator, and growing chain free radical, to the reversible addition of carbon sulphur double bond in two sulfur ester molecule, forms new spike, thus further effectively trigger monomer be polymerized.Because the speed of addition or fracture is more faster than the speed of chainpropagation, two sulfur ester shifts rapidly between living radical and dormancy free radical, makes molecular weight distribution sharp, thus makes polymerization embody controlled/living features.
RAFT polymerization process has successfully achieved the polymerization of AA and AMPS under non-aqueous conditions, as CN102796234A discloses a kind of preparation method of polycarboxylic-acid cement grinding aid, by unsaturated polyether, unsaturated sulfonic acid, unsaturated carboxylic acid and RAFT agent and dehydrated alcohol mixing, add again and draw the agent aqueous solution, be made into emulsion; By initiator and water wiring solution-forming; Under intensification heating condition, drip solution in emulsion, after reaction, polycarboxylic acid series grinding aid finished product is prepared in neutralization.
In the existing aqueous solution RAFT living polymerization report in, though successfully achieve the aqueous solution living polymerization of acrylic amide various of monomer, vinylformic acid and maleic acid monomer, and the molecular weight distribution of polymkeric substance is controlled preferably, but less to the aqueous solution RAFT polymerization studies report of acid monomer.
Summary of the invention
For solving the deficiency of above-mentioned RAFT polymerization process, preparation narrow molecular weight distribution, number-average molecular weight is less than the AA-AMPS multipolymer of 10,000, the object of the present invention is to provide a kind of RAFT method water react to prepare the method for the AA-AMPS multipolymer of narrow molecular weight distributions, the number-average molecular weight of the sodium salt derivative of prepared multipolymer is 5200 to 10000.
Another object of the present invention is to provide a kind of aqueous phase system, simple, and temperature of reaction is low, and the reaction times is short, the RAFT reactive polymeric method that reaction yield is high, to eliminate at least some defect of prior art.
Technical scheme of the present invention is as follows:
A method for the vinylformic acid prepared under aqueous phase condition and 2-acrylamide-2-methyl-propane sulfonic acid multipolymer sodium salt derivative, comprises the following steps:
1) add vinylformic acid, 2-acrylamide-2-methyl-propane sulfonic acid, RAFT reagent and deionized water and stirring in the reactor to dissolve;
2) be heated to 50 DEG C to 70 DEG C, slowly drip the persulfide aqueous solution;
3), after the aqueous solution of superoxide dropwises, stirring 6 to 8 hours is continued;
4) be cooled to room temperature, in reactor, add the 10%NaOH aqueous solution, regulate pH to be 8 to 9;
5) revolve to boil off to desolventize and obtain vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid multipolymer sodium salt derivative.
Method of the present invention, the quality of described 2-acrylamide-2-methyl-propane sulfonic acid accounts for 40% to 70% of vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid total mass.
Method of the present invention, the mass ratio of described RAFT reagent and persulfide is 1.25:1.The ratio of the quality of RAFT reagent and vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid total mass is 3:100 to 6:100.
Method of the present invention, the ratio of the quality of described persulfide and vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid total mass is 2.5:100 to 5:100.
Method of the present invention, before the described dropping persulfide aqueous solution, in reactor, the ratio of deionized water quality and vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid total mass is 2:1 to 5:1.
Method of the present invention, described persulfide is selected from Potassium Persulphate, Sodium Persulfate, one or more mixture of ammonium persulphate, and the mass concentration of its aqueous solution is 0.1 grams per milliliter.
Method of the present invention, the time for adding of the described persulfide aqueous solution is 15 to 20 minutes.
Method of the present invention, described RAFT reagent is selected from two (carboxyalkyl) trithiocarbonate, has following structural formula:
Method of the present invention, the number-average molecular weight of described vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid multipolymer sodium salt derivative is 5200 to 10000; The molecular weight distribution of described vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid multipolymer sodium salt derivative is 1.60 to 1.85.By technique scheme, the advantage that the present invention has and beneficial effect are:
1, the invention provides a kind of simple, that the reaction rate of recovery is high method and prepare the polymkeric substance containing sulfonate group and carboxylate group.
2, the invention provides one simple, the method that the reaction rate of recovery is high prepares the polymkeric substance of molecular weight distribution below 2.0.
3, the invention provides a kind of simple, the method that the reaction rate of recovery is high prepare molecular weight 5200 to 10000 the polymkeric substance containing hydrophilic radical.
Embodiment
For a person skilled in the art, by reading the disclosure of the specification, feature of the present invention, beneficial effect and advantage will become apparent.
Except as otherwise noted, all per-cent, mark and ratio are all the total weight by the present composition.Except as otherwise noted, all wt about ingredients listed all gives the content of active substance, therefore their solvents that may comprise not included in the material of commercially available acquisition or by product.Term " weight content " available symbols " % " represents herein.
Except as otherwise noted, all in this article molecular weight are all relative molecular mass.
Except as otherwise noted, all preparations and test occur in the environment of 25 DEG C in this article.
" comprise " herein, " comprising ", " containing ", " containing ", " having " or other variant be intended to contain non-enclosed comprising, do not distinguish between these terms.Term " comprises " other step and composition of referring to and can adding and not affect net result.Term " comprise " also comprise term " by ... composition " and " substantially by ... form ".The compositions and methods of the invention/technique can comprise, consisting of be substantially made up of bioelement described herein and limit entry and arbitrary additional or optional composition, component, step or limit entry described herein.
polymerization system
The polymerization system that the present invention relates to refers to and comprises monomer, initiator, free radical, chain-transfer agent, reaction medium, the reaction system of polymkeric substance.
monomer
The monomer that the present invention relates to, or claim polymerization single polymerization monomer, be containing unsaturated link(age), under certain condition, can structural unit be formed, and repeat the compound being connected to form polymkeric substance.
Monomer specifically refers to vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid.The present invention represents the structural unit of vinylformic acid and formation thereof with AA, and AMPS represents the structural unit of 2-acrylamide-2-methyl-propane sulfonic acid and formation thereof.
polymkeric substance
The polymkeric substance that the present invention relates to, refers to the compound that the structural unit formed by monomer repeats to be connected to form and derivative thereof.
The polymkeric substance that the present invention relates to specifically refers to multipolymer and the sodium salt derivative thereof of vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid.The present invention represents the multipolymer of vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid with AA-AMPS polymkeric substance.
The sodium salt derivative of AA-AMPS polymkeric substance contains sulfonate group and carboxylate group, and these two kinds of groups are all the good groups of wetting ability.
initiator
The initiator that the present invention relates to refers to the compound that can produce trigger monomer generation polymer reaction under certain condition.Described " certain condition " refers to that temperature raises, or ultraviolet light irradiation etc., corresponding initiator is called thermal initiator, light trigger.
According to the type of the spike that initiator produces, initiator can be divided into free radical type initiator, cationic initiators, anionic initiator etc.
The initiator that the present invention relates to specifically refers to thermal radical type initiator, and this compounds can produce the polymerization of primary activity free radical thus trigger monomer in a heated condition.
Thermal radical type initiator of the present invention is selected from Potassium Persulphate, Sodium Persulfate, one or more mixture of ammonium persulphate.
chain-transfer agent
The chain-transfer agent that the present invention relates to refers to the compound that obviously can affect polymericular weight and distribution.Chain-transfer agent by and combined with radical and change the kind of free radical, thus reach the object of regulate polymer molecular weight.
Common chain-transfer agent is as lauryl mercaptan.
reaction medium
The reaction medium that the present invention relates to refers to monomer, initiator, chain-transfer agent, and the compound of the polymer uniform dispersion of reaction generation.In in this law, " reaction medium " and " reaction solvent " is equal to completely, does not distinguish.
Common reaction medium comprises organic solvent as ketone, arene, sulfone class etc., and water.Water is wherein used to be called that aqueous polymerization reacts as the polyreaction of reaction medium.
free radical
The free radical that the present invention relates to refers to containing azygous electronics, can and monomer carry out the material of quick addition reaction.According to the difference of type, the free radical in polymerization system comprises the primary group of free radicals that decomposition of initiator produces, and monomer and primary group of free radicals combine the propagating radical produced, the free radical etc. that chain transfer reaction produces.Wherein propagating radical and monomer addition repeatedly, until the generation of polymkeric substance.
polyreaction
The polyreaction that the present invention relates to refers to that monomer forms structural unit, and repeats the process being connected to form polymkeric substance.
Polyreaction can be divided into chain polymerization to react and the large classification of step-reaction polymerization two.Chain polymerization reaction is different according to mechanism, is divided into Raolical polymerizable, ionic polymerization, coordinates polyreaction etc.
The polyreaction that the present invention relates to specifically refers to aqueous phase radical chain polyreaction.
radical chain polymerization reaction mechanism
The polymerization reaction mechanism that the present invention relates to is specific as follows:
Chain starting reaction:
I→I*；
I*+M→M*；
Transfer reaction:
M
n*+M→M
n+1*；
Chain transfer reaction:
M
n*+A→M
n+A*；
Chain termination reaction:
M
n*+M
m* → M
m+nor M
n+ M
m;
M
n*+A*→M
n-A；
Wherein: I is initiator, I* is called elementary initiation free radical, and M is monomer, n and m represents the repetition number of the structural unit that monomer is formed, M*, M
n*, M
m* propagating radical is claimed, or growing chain.A be can with the compound of free radical generation chain transfer reaction.A* is the free radical that chain transfer reaction produces.
reversible addion-fragmentation chain transfer polymerization and RAFT reagent
The reversible addion-fragmentation chain transfer polymerization (ReversibleAddition-FragmentationChainTransferPolymerizat ion calls RAFT polymerization in the following text) that the present invention relates to is a kind of Raolical polymerizable.It uses RAFT reagent.
The RAFT reagent that the present invention relates to is a kind of chain-transfer agent, its can and propagating radical generation there is chain transfer reaction rapidly, thus the number of growing chain is maintained a comparatively stable level.This chain transfer reaction is reversible, the addition of propagating radical and RAFT reagent produces stable, the chain tra nsfer free radical (nonactive free radical) of more difficult and monomer generation addition reaction, thus effectively avoid the double-basis termination reaction between propagating radical.This stable chain tra nsfer free radical (nonactive free radical) can decompose the cracking free radical (living radical) producing energy and monomer generation addition reaction under certain condition again.
The RAFT reagent that the present invention relates to is the one of chain-transfer agent.RAFT reagent is selected from two (carboxyalkyl) trithiocarbonate, has following structural formula:
In some following synthetic schemess, RAFT reagent is two carboxymethyl trithiocarbonates.
reversible addion-fragmentation chain transfer polymerization reaction mechanism
The RAFT polymerization reaction mechanism that the present invention relates to is specific as follows:
Chain starting reaction:
I→I*；
I*+M→I-M*；
Transfer reaction:
I-M*+M→→M
n*；
M
n*+M→M
n+1*；
Chain transfer reaction:
M
n*+A→M
n+A*；
Reversible chain transfer reaction/per-equilibrium reaction:
Chain starting reaction again
R*+M→R-M*；
Reversible chain balanced reaction/main balanced reaction:
Chain termination reaction:
M
n*+M
m* → M
m+nor M
n+ M
m;
M
n*+A*→M
n-A；
M
n*+R*→M
n-R；
Wherein: I is initiator, I* is called elementary initiation free radical, and M is monomer, n and m represents the repetition number of the structural unit that monomer is formed, M*, M
n*, M
m* propagating radical is claimed, or growing chain.A be can with the compound of free radical generation chain transfer reaction.A* is the free radical that chain transfer reaction produces.
RAFT reagent example is two thioes derivatives, and structure is as follows:
R is the organic group replaced by one or more hydrophilic radicals, and Z, for can promote that thiocarbonyl and free radical fully react, does not make fracture cannot any group of acceptance level to making polyreaction be deferred to simultaneously.
the molecular weight of polymkeric substance and molecular weight distribution thereof
Polymkeric substance is that a series of molecular size range differs, and has the mixture of the homologue composition of same structure unit.The molecular-weight average of polymkeric substance is a statistical value.Be called number-average molecular weight with the molecular weight of the average polymkeric substance of molecule amount, represent with Mn.Be called weight-average molecular weight with the molecular weight of the average polymkeric substance of quality, represent with Mw.
In polymkeric substance, homologue molecular weight difference each other molecular weight distribution (D) characterizes.D value is calculated as follows:
During D=1.0, the molecular weight distribution of polymkeric substance has the polymkeric substance of monodispersity, and its number-average molecular weight is identical with weight-average molecular weight; Namely all in polymkeric substance homologue molecular weight are identical.
The D value of polymkeric substance is generally all greater than 1.0.D value is less, and molecular weight difference is more close each other for the homologue illustrating in polymkeric substance; Molecular weight difference is larger each other for D value larger explanation homologue.
An object of the present invention obtains the less polymkeric substance of D value as far as possible.
the polymkeric substance of narrow molecular weight distributions
The polymkeric substance of the narrow molecular weight distributions that the present invention relates to refer to molecular weight distribution 2.0 polymkeric substance.Particularly, narrow molecular weight distributions refers to that D value is 1.60 to 1.85.
the polymkeric substance of lower molecular weight
The polymkeric substance of the lower molecular weight that the present invention relates to is the polymkeric substance of number average molecular below 10000.Particularly, lower molecular weight is that number average molecular is between 5000 to 10000.
the testing method of polymericular weight and distribution thereof
The present invention selects gel exclusion chromatography (GPC) to measure the molecular mass and distribution of polymkeric substance.Aqueous phase GPC is specifically adopted to carry out molecular weight determination.
Aqueous phase refers to that GPC test adopts water as moving phase.Differential refraction detector (RID) is adopted to detect.
The present invention adopts the polyacrylic acid molecular weight standards of German PSS company (PolymerStandardServiceGmbH), and the number-average molecular weight of standard substance is between 1000 to 20000.
the water dissolution performance of polymkeric substance
The water dissolution performance of the polymkeric substance that the present invention relates to specifically refers to: the solvability of 25 grams of polymkeric substance in 100 grams of deionized waters.
Dissolution time is 5 minutes.Solubility property adopts visual method to determine.Solubility property grade evaluation is as shown in table 1.
The evaluation of table 1 solubility property and grade
Without the need to further describing, believe that those skilled in the art use the above can use the present invention to greatest extent.The following examples object is introduce further and show specific embodiments within the scope of the present invention.Therefore, embodiment is interpreted as only for showing the present invention in more detail, and the content do not limited the present invention in any way.
In following examples, except as otherwise noted, all content is all weight percentages, and the content about ingredients listed is through the content of the active substance of conversion.
the preparation embodiment 1-6 of the sodium salt derivative of AA-AMPS polymkeric substance and comparative example 1-3
The composition being polymerization system with following table 2 and the name of embodiment.
The composition of table 2 embodiment 1-6 and comparative example 1-3 polymerization system
1) add 2-acrylamide-2-methylpro panesulfonic acid, vinylformic acid, two (carboxymethyl) trithiocarbonate in the reactor, add 60 grams of deionized waters, be stirred to and dissolve completely;
2) be warming up to 60 DEG C, Potassium Persulphate be dissolved in dissolving in 5 grams of deionized waters and obtain potassium persulfate solution;
3) in reactor, drip persulfate aqueous solution, time for adding controls at 10 minutes to 15 minutes, and dropwise rear continuation stirring reaction, temperature keeps 60 DEG C.React and be cooled to room temperature after 6 hours;
4) in reactor, add the 10%NaOH aqueous solution, regulate pH to 8.5;
5) be warming up to 100 DEG C of vacuum rotary steams, remove solvent and obtain vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid multipolymer sodium salt derivative.
the molecular size range of the sodium salt derivative of AA-AMPS polymkeric substance and the test of distribution
Adopt AglilentPLaquagel-OH30,8 μm of gel chromatographic columnses carry out molecular weight test, adopt differential refraction detector (RID) as detection part, adopt AgilentGPC software to carry out interpretation of result.
Moving phase is the trisodium phosphate aqueous solution of 0.02mol/L, and flow velocity is 1mL/min, and column temperature is 35 DEG C.Molecular weight standards is the polyacrylic acid standard substance of German PSS company (PolymerStandardServiceGmbH), and its number-average molecular weight is between 1000 to 20000.
Take different molecular weight polyacrylic acid standard substance 30 milligrams in 10 milliliters of volumetric flasks, add ultrapure water and be settled to scale, obtained series standard solution.Take 30 milligrams, AA-AMPS multipolymer sodium salt derivative sample in 10 milliliters of volumetric flasks, add ultrapure water and be settled to scale, obtained sample solution.
The molecule measuring test result of embodiment 1-6 and comparative example 1-3 listed by table 3.
The molecule measuring test result of table 3 embodiment 1-6 and comparative example 1-3
From the content of above-mentioned table 3, AA-AMPS multipolymer sodium salt derivative number-average molecular weight prepared by embodiment of the present invention 1-6 5200 to 10000, molecular weight distribution 1.60 to 1.85.And AA-AMPS multipolymer sodium salt derivative number-average molecular weight prepared by comparative example 1-3 is not in 5200 to 10000 scopes, molecular weight distribution is wider.
the solubility property test of the sodium salt derivative of AA-AMPS polymkeric substance
Solubility property testing method is by the solvability of the sodium salt derivative of 25 grams of AA-AMPS polymkeric substance in 100 grams of deionized waters.
Dissolution time is 5 minutes.Solubility property grading is as shown in table 4 below.Solubility property adopts visual method to determine.Dissolve the result of test as table 4 data.
The solubility property of the sodium salt derivative of table 4AA-AMPS polymkeric substance
| AA-AMPS multipolymer sodium salt derivative | Solubility property | |
| Embodiment 1 | Copolymer A | Dissolve completely |
| Embodiment 2 | Multipolymer B | Dissolve completely |
| Embodiment 3 | Multipolymer C | Dissolve completely |
| Embodiment 4 | Multipolymer D | Dissolve completely |
| Embodiment 5 | Multipolymer E | Dissolve completely |
| Embodiment 6 | Multipolymer F | Dissolve completely |
From the content of above-mentioned table 4, the sodium salt derivative of AA-AMPS polymkeric substance prepared by embodiment of the present invention 1-6 has good solubility energy.
Dimension disclosed herein and numerical value should not be construed as the strict restriction of described exact value.Unless otherwise indicated, each such dimension is intended to represent described value and the functionally equivalent scope around this value.Such as, the dimension being disclosed as " 40mm " is intended to represent " about 40mm ".
The All Files quoted in summary of the invention is all included in herein with way of reference in relevant portion.Should not be interpreted as admitting that it is prior art for the present invention for quoting of any file.
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, therefore everyly do not depart from technical solution of the present invention content, the any simple modification done above embodiment according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (11)
1. prepare a method for vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid multipolymer sodium salt derivative, it is characterized in that, the method comprises the following steps:
1) add vinylformic acid, 2-acrylamide-2-methyl-propane sulfonic acid, RAFT reagent and deionized water and stirring in the reactor to dissolve;
2) be heated to 50 DEG C to 70 DEG C, slowly drip the persulfide aqueous solution;
3), after the persulfide aqueous solution dropwises, stirring 6 to 8 hours is continued;
4) be cooled to room temperature, in reactor, add the 10%NaOH aqueous solution, regulate pH to be 8 to 9;
5) revolve to boil off to desolventize and obtain vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid multipolymer sodium salt derivative.
2. the method for claim 1, is characterized in that: the quality of described 2-acrylamide-2-methyl-propane sulfonic acid accounts for 40% to 70% of vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid total mass.
3. the method for claim 1, is characterized in that: the mass ratio of described RAFT reagent and persulfide is 1.25:1.
4. the method for claim 1, is characterized in that: the mass ratio of described RAFT reagent and vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid total mass is 3:100 to 6:100.
5. the method for claim 1, is characterized in that: the mass ratio of described persulfide and vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid total mass is 2.5:100 to 5:100.
6. the method for claim 1, is characterized in that: before the described dropping persulfide aqueous solution, in reactor, the ratio of deionized water quality and vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid total mass quality is 2:1 to 5:1.
7. the method for claim 1, is characterized in that: the mass concentration of the described persulfide aqueous solution is 0.1 grams per milliliter.
8. the method for claim 1, is characterized in that: described persulfide is selected from Potassium Persulphate, Sodium Persulfate, one or more mixture of ammonium persulphate.
9. the method for claim 1, is characterized in that: described RAFT reagent is selected from two (carboxyalkyl) trithiocarbonate, has following structural formula:
Wherein, a and b is 1,2,3.
10. the method for claim 1, is characterized in that: the time for adding of the described persulfide aqueous solution is 15 to 20 minutes.
11. the method for claim 1, is characterized in that: the number-average molecular weight of described vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid multipolymer sodium salt derivative is 5200 to 10000; The molecular weight distribution of described vinylformic acid and 2-acrylamide-2-methyl-propane sulfonic acid multipolymer sodium salt derivative is 1.60 to 1.85.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106674411A (en) * | 2017-01-12 | 2017-05-17 | 浙江万里学院 | Synthesis method of high-water-absorptivity resin |
| CN111004344A (en) * | 2019-12-20 | 2020-04-14 | 北京化工大学 | Method for regulating and controlling maximum critical miscible temperature of zwitterionic polymer through end group modification |
| CN113831444A (en) * | 2021-09-29 | 2021-12-24 | 湖北海力环保科技股份有限公司 | Method and device for synthesizing narrow-distribution medium-low molecular weight AA/AMPS copolymer |
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| CN102070742A (en) * | 2010-12-22 | 2011-05-25 | 广州立白企业集团有限公司 | Method for synthesizing acrylic acid-maleic anhydride copolymer in aqueous phase by RAFT method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674411A (en) * | 2017-01-12 | 2017-05-17 | 浙江万里学院 | Synthesis method of high-water-absorptivity resin |
| CN111004344A (en) * | 2019-12-20 | 2020-04-14 | 北京化工大学 | Method for regulating and controlling maximum critical miscible temperature of zwitterionic polymer through end group modification |
| CN113831444A (en) * | 2021-09-29 | 2021-12-24 | 湖北海力环保科技股份有限公司 | Method and device for synthesizing narrow-distribution medium-low molecular weight AA/AMPS copolymer |
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